Polyestercarbonate from spiro dihydric phenol

ABSTRACT

Polycarbonates exhibiting improved heat distortion temperatures which are comprised of the polymerized coreaction products of (i) a carbonate precursor, and (ii) at least one particular spiro dihydric phenol.

This is a division of copending application Ser. No. 544,004, filed Oct.21, 1983, now U.S. Pat. No. 4,552,949.

BACKGROUND OF THE INVENTION

Polycarbonates are well known thermoplastic materials which, due totheir many advantageous properties, find use as thermoplasticengineering materials in many commercial and industrial applications.The polycarbonates exhibit, for example, excellent properties oftoughness, flexibility, impact resistance and high heat distortiontemperatures. The polycarbonates and their preparation are disclosed,for example, in U.S. Pat. Nos. 3,028,365; 3,334,154; 3,275,601 and3,915,926.

There is, however, a need in certain applications, such as thoseinvolving a high temperature environment, for polycarbonates exhibitingeven higher heat distortion temperatures than those possessed bypresently available polycarbonates. It is known to increase the heatdistortion temperatures of polycarbonates by adding thereto variouspolymer systems which exhibit high heat distortion temperatures such aspolyarylates, polysulfones, and the like. These resulting blends,however, suffer from certain disadvantages such as being opaque,undergoing phase separation and delamination, and loss of certain uniqueproperties of unblended polycarbonates such as impact strength and thelike.

There thus exists a need for polycarbonates exhibiting improved heatdistortion temperatures while simultaneously retaining, to a substantialdegree, substantially most of the other advantageous properties ofconventional polycarbonates. It is, therefore, an object of the instantinvention to provide polycarbonates exhibiting improved heat distortiontemperatures.

SUMMARY OF THE INVENTION

In accordance with the instant invention there are provided novelpolycarbonates exhibiting improved heat distortion temperatures. Thesepolycarbonates are derived from (i) a carbonate precursor, and (ii) atleast one particular spiro dihydric phenol.

DESCRIPTION OF THE INVENTION

According to the present invention there are provided polycarbonatesexhibiting improved heat distortion temperatures while simultaneouslyexhibiting, to a substantial degree, substantially most of the otheradvantageous properties of conventional polycarbonates such astoughness, flexibility, optical clarity, impact strength, and the like.

These novel polycarbonates are derived from, as essential reactants, (i)a carbonate precursor, and (ii) at least one spiro dihydric phenolselected from spiro dihydric phenols represented by the general formula##STR1## wherein: R is independently selected from monovalenthydrocarbon radicals and halogen radicals: and

n is independently selected from positive integers having a value offrom 0 to 3 inclusive.

The monovalent hydrocarbon radicals represented by R include the alkylradicals, the cycloalkyl radicals, the aryl radicals, the aralkylradicals, and the alkaryl radicals.

The alkyl radicals represented by R are preferably those containing from1 to about 12 carbon atoms. These include the branched alkyl radicalsand the straight chain alkyl radicals. Some illustrative non-limitingexamples of these alkyl radicals include methyl, ethyl, propyl,isopropyl, butyl, tertiary-butyl, pentyl, neopentyl, and hexyl.

The cycloalkyl radicals represented by R are preferably those containingfrom 4 to about 7 ring carbon atoms. These include cyclobutyl,cyclopentyl, cyclohexyl, methylcyclohexyl, and cycloheptyl.

The aryl radicals represented by R are preferably those containing from6 to 12 ring carbon atoms. These include phenyl, biphenyl, and naphthyl.

Preferred aralkyl and alkaryl radicals represented by R are thosecontaining from 7 to about 14 carbon atoms. These include, but are notlimited to, benzyl, ethylphenyl, phenylbutyl, phenylpropyl,propylphenyl, and phenylethyl,

The preferred halogen radicals represented by R are chlorine andbromine.

Preferably R is independently selected from chlorine, bromine, and loweralkyl radicals containing from 1 to about 5 carbon atoms.

In the dihydric phenol compound of Formula I when more than one Rsubstituent is present they may be the same or different. The positionsof the hydroxyl groups and R on the aromatic nuclear residues may bevaried in the ortho or meta positions.

The spiro dihydric phenols of Formula I are compounds that are known inthe art and are commercially available or may be readily prepared byknown methods. These methods of preparation of the spiro dihydricphenols of Formula I include those described by R. F. Curtis and K. O.Lewis in Journal of the Chemical Society (England), 1962, p. 420, and R.F. Curtis in Journal of the Chemical Society (England), 1962, p. 417.

These spiro dihydric phenols may be conveniently prepared by (i)reacting two moles of a phenol with one mole of acetone, and (ii)thereafter coreacting 3 moles of the product of (i) under acidicconditions to form the spiro dihydric phenols of Formula I and 4 molesof a phenol. The acids which may be utilized in (ii) can include suchacids as anhydrous methane sulfonic acid, anhydrous hydrochloric acid,and the like.

Some illustrative non-limiting examples of the spiro dihydric phenols ofFormula I include: ##STR2##

It is, of course, possible to employ mixtures of two or more dihydricphenols of Formula I if a carbonate copolymer rather than a homopolymeris desired.

The carbonate precursor may be a carbonyl halide, a bishaloformate or adiarylcarbonate. The carbonyl halides include carbonyl chloride,carbonyl bromide, and mixtures thereof. The bishaloformates include thebishaloformates of dihydric phenols such as bischloroformates of2,2-bis(4-hydroxphenyl)propane,2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, hydroquinone, and thelike, or the bishaloformates of glycols such as the bischloroformates ofethylene glycol, neopentyl glycol, polyethylene glycol, and the like.Typical of the diarylcarbonates which may be employed are diphenylcarbonate; di-(halophenyl)carbonates such as di-(chlorophenyl)carbonate,di-(bromophenyl)carbonate, di-( trichlorophenyl)carbonate,di-(tribromophenyl) carbonate, and the like; di-(alkylphenyl)carbonatessuch as di-(tolyl)carbonate, and the like. Some other illustrativenon-limiting examples of suitable diarylcarbonates includedi-(naphthyl)carbonate, di-(chloronaphthyl)carbonate, phenyl tolylcarbonate, chlorophenyl chloronaphthyl carbonate, and the like.

The preferred carbonate precursors are the carbonyl halides, withcarbonyl chloride, also known as phosgene, being the preferred carbonylhalide.

One method which may be employed in preparing the polycarbonates of theinstant invention involves the heterogeneous interfacial polymerizationsystem utilizing an aqueous caustic solution, an organic waterimmiscible solvent, at least one dihydric phenol of Formula I, acatalyst, a carbonate precursor, and a molecular weight regulator. Apreferred heterogeneous interfacial polymerization system is one whichutilizes phosgene as the carbonate precursor.

Another useful method for preparing the carbonate polymers of theinstant invention involves the use of an organic solvent system whereinthe organic solvent system may also function as an acid acceptor, atleast one dihydric phenol of Formula I, a molecular weight regulator,and a carbonate precursor. A preferred method is one wherein phosgene isutilized as the carbonate precursor.

Generally, in both of the aforedescribed methods phosgene is passed intoa reaction mixture which contains at least one dihydric phenol ofFormula I. The temperature at which the phosgenation reaction proceedsmay vary from below 0° C. to above 100° C. The reaction proceedssatisfactorily at temperatures from room temperature (25° C.) to about50° C. Since the reaction is exothermic, the rate of phosgene additionmay be used to control the reaction temperature.

A suitable acid acceptor may be either organic or inorganic in nature. Asuitable organic acid acceptor is a tertiary amine and includes suchmaterials as pyridine, triethylamine, tributylamine, dimethylaniline,trimethylpyridine, etc. The inorganic acid acceptor may be a hydroxide,such as an alkali or alkaline earth metal hydroxide, a carbonate, abicarbonate, a phosphate, and the like. An inorganic acid acceptor ispreferred when an aqueous solvent system is used.

The catalysts which may be employed can be any of the well knowncatalysts which aid the polymerization reaction of the dihydric phenolwith phosgene. Suitable catalysts include, but are not limited to,tertiary amines, secondary amines, quaternary ammonium compounds,quaternary phosphonium compounds, amidines, and the like.

The molecular weight regulators employed may be any of the knowncompounds which regulate the molecular weight of the carbonate polymersby a chain stopping or terminating mechanism. These compounds include,but are not limited to, phenol, tertiarybutyl phenol, and the like.

The amount of phosgene utilized is an amount effective to react withsubstantially all of the unreacted hydroxyl groups present on thenuclear aromatic residues of the dihydric phenols of Formula I. Thisamount is referred to as a stoichiometric amount.

The high molecular weight aromatic carbonate polymers of the instantinvention generally have a weight average molecular weight in the rangeof from about 5,000 to about 200,000, preferably from about 10,000 toabout 100,000, and more preferably from about 25,000 to about 50,000.

The polycarbonates of the instant invention will contain at least onerepeating structural unit represented by the general formula ##STR3##wherein R and n are as defined hereinafore.

If only one dihydric phenol of Formula I is used than the polycarbonateswill contain only one repeating structural unit of Formula II. If morethan one dihydric phenol of Formula I is used the instant polycarbonateswill contain more than one repeating structural unit of Formula II, thenumber and type of structural units being dependant on the number andtype of dihydric phenols employed.

The polycarbonates of the instant invention may optionally have admixedtherewith the commonly known and used additives such as, for example,antistatic agents; mold release agents; impact modifiers; inert fillerssuch as glass, talc, mica, and clay; ultraviolet radiation absorberssuch as the benzophenones, benzotriazoles, and benzylidene malonates;hydrolytic stabilizers such as the epoxides disclosed in U.S. Pat. Nos.3,489,716, 4,138,379 and 3,839,247, all of which are hereby incorporatedherein by reference; color stabilizers such as the organophosphitesdisclosed in U.S. Pat. Nos. 3,305,520 and 4,118,370, both of which areincorporated herein by reference; and flame retardants.

Some particularly useful flame retardants include the alkali andalkaline earth metal salts of sulfonic acids. These types of flameretardants are disclosed in U.S. Pat. Nos. 3,933,734, 3,948,851,3,926,908, 3,919,176, 3,909,490, 3,953,396, 3,931,100, 3,978,024,3,953,399, 3,917,559, 3,951,910 and 3,940,366, all of which areincorporated herein by reference.

Another embodiment of the instant invention is a carbonate copolymerobtained by coreacting (i) a carbonate precursor, (ii) at least onespiro dihydric phenol of Formula I, and (iii) a conventional non-spirodihydric phenol.

The non-spiro dihydric phenols are well known in the art and aredisclosed, for example, in U.S. Pat. Nos. 3,028, 3,169,121, 3,275,601and 4,111,910, all of which are incorporated herein by reference.

These non-spiro dihydric phenols will in general conform to the generalformula ##STR4## wherein: R¹ is independently selected from monovalenthydrocarbon radicals and halogen radicals;

a is independently selected from positive integers having a value offrom 0 to 4 inclusive;

d is either zero or one; and

W is selected from divalent hydrocarbon radicals; --S--, --O--,--S--S--, ##STR5##

The monovalent hydrocarbon radicals represented by R¹ include the alkylradicals, the cycloalkyl radicals, the aryl radicals, the aralkylradicals, and the alkaryl radicals. The carbon atom limitations for eachgroup are the same as for the aforementioned R group of Formula I. R¹ ispreferably chloro, bromo, or alkyl of one to five carbon atoms,inclusive.

The divalent hydrocarbon radicals represented by W include the alkyleneradicals of two to ten carbon atoms, the cycloalkylene radicals of fourto seven carbon atoms, the alkylidene radicals of two to ten carbonatoms, and the cycloalkylidene radicals of four to seven carbon atoms.These divalent hydrocarbon radicals are the non-spiro radicals.

In the dihydric phenols represented by Formula III when more than one R¹substituent is present they may be the same or different. Where d iszero in Formula III the aromatic rings are directly joined with nointervening alkylene or other bridge. The positions of the hydroxylgroups and R¹ on the aromatic nuclear residues can be varied in theortho, meta, or para positions and the groupings can be in a vicinal,asymmetrical or symmetrical relationship where two or more ring carbonatoms of the aromatic hydrocarbon residues are substituted with R andhydroxyl group.

Some illustrative non-limiting examples of dihydric phenols of FormulaIII include:

2,2-bis(4-hydroxyphenyl)propane (bisphenol-A);

4,4'-dihydroxydiphenylmethane;

1,2-bis(4-hydroxyphenyl)ethane;

2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane;

1,1-bis(4-hydroxy-3-chlorophenyl)ethane;

2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane;

4,4-thiodiphenol; and

1,1-bis(4-hydroxyphenyl)cyclohexane.

It is, of course, possible to employ a mixture of two or more differentdihydric phenols of Formula III in preparing the copolycarbonates of theinstant invention.

The copolycarbonates of this embodiment are prepared by coreacting (i) acarbonate precursor, (ii) at least one spiro dihydric phenol of FormulaI, and (iii) at least one non-spiro dihydric phenol of Formula III insubstantially the same manner and under substantially the same reactionconditions as described hereinafore.

The copolycarbonates of this embodiment will contain at least onerepeating structural unit of Formula II and at least one repeatingstructural unit represented by the general formula ##STR6## wherein R¹,W, a and d are as defined hereinafore.

The amount of the spiro dihydric phenol of Formula I employed inproducing the copolycarbonates of this embodiment is an amount effectiveto improve the heat distortion temperatures of the copolycarbonates.That is to say, the copolycarbonates of this invention contain an amountof repeating structural units of Formula II effective to improve theheat distortion temperatures of the copolycarbonates. Generally, thisamount is at least about 3 mole percent, based on the total amount ofthe repeating structural units of Formula II and Formula IV present.That is to say, the amount of the spiro dihydric phenol of Formula Iemployed in producing the instant copolycarbonates is at least about 3mole percent, based on the total amounts of the spiro dihydric phenol ofFormula I and the non-spiro dihydric phenol of Formula III used.

Generally, if the copolycarbonates of this embodiment contain less thanabout 3 mole percent of the repeating structural units of Formula IIthere will be no significant improvement in the heat distortiontemperatures of the copolycarbonates, i.e., if less than about 3 molepercent of the spiro dihydric phenol of Formula I is used there willgenerally be no significant improvement in the heat distortiontemperatures of the resultant copolycarbonates.

The upper limit of the amounts of the repeating structural units ofFormula II present, i.e., the upper limit of the amount of the spirodihydric phenol utilized, is not critical, but is instead governed bysuch secondary considerations as cost and the like. Generally, it ispreferred to use no more than about 95 mole percent of the spirodihydric pheol of Formula I, i.e., it is preferred that thecopolycarbonates contain no more than about 95 mole percent of repeatingstructural units of Formula II.

Also included with the scope of this invention are the high molecularweight thermoplastic randomly branched polycarbonates. These randomlybranched polycarbonates may be obtained by the incorporation of smallamounts, prefereably between 0.05 and 2.0 mol percent (based on thequantity of the dihydric phenols used), of polyfunctional, i.e.,trifunctional or greater, organic compounds, particularly compoundswhich have three or more phenolic hydroxyl groups. The polyfunctionalorganic compounds which may be used to form the randomly branchedpolycarbonates are disclosed in U.S. Pat. Nos. 3,635,895; 4,001,184; and3,544,514, all of which are hereby incorporated herein by reference.These polyfunctional compounds are generally aromatic and contain atleast three functional groups which may be carboxyl, hydroxyl,carboxylic anhydride, haloformyl, or mixtures thereof. Some illustrativenon-limiting examples of these polyfunctional compounds includetrimellitic anhydride, trimellitic acid, trimellityl trichloride,4-chloroformyl phthalic anhydride, pyromellitic acid, pyromelliticdianhydride, mellitic acid, mellitic anhydride, trimesic acid,benzophenonetetracarboxylic acid, and the like.

Yet another embodiment of the instant invention is a polycarbonate blendcomprised of (i) at least one carbonate polymer obtained by the reactionof at least one dihydric phenol of Formula I with a carbonate precursor,and (ii) at least one carbonate polymer obtained by the reaction of atleast one dihydric phenol of Formula III with a carbonate precursor.

These polycarbonate blends are generally formed by first preforming thevarious carbonate polymers and thereafter physically mixing or blendingthe various carbonate polymers together.

The polycarbonate blends of this embodiment generally contain an amountof at least one carbonate polymer derived from the spiro dihydric phenolof Formula I effective to improve the heat distortion temperatures ofthe blends. Generally, this amount is at least about 3 weight percent,based on the total amounts of the polycarbonate derived from the spirodihydric phenol of Formula I and the polycarbonate derived from thenon-spiro dihydric phenol of Formula III present. In general, if theseblends. contain less than about 3 weight percent of the polycarbonatederived from the spiro dihydric phenol there will be no significantimprovement in their heat distortion temperatures. The upper limit ofthe amount of the polycarbonate derived from the spiro dihydric phenolof Formula I is not critical but is controlled by such secondaryconsiderations as cost and the like. Generally, it is preferred thatthese blends contain no more than about 95 weight percent of thepolycarbonate derived from the spiro dihydric phenol of Formula I.

The instant blends may optionally have admixed therewith theaforedescribed commonly known and used additives.

Still another embodiment of the instant invention are thecopolyester-carbonates of the spiro dihydric phenols of Formula I.

Briefly stated, the copolyester-carbonates of this embodiment compriserecurring carbonate groups ##STR7## carboxylate groups ##STR8## andaromatic carbocyclic groups in the polymer chain, in which at least someof the carboxylate groups and at least some of the carbonate groups arebonded directly to ring carbon atoms of the aromatic carbocyclic groups.

These copolyester-carbonates contain ester bonds and carbonate bonds inthe polymer chain wherein the amount of ester bonds is in the range offrom about 25 to about 90 mole percent, and preferably from about 35 toabout 80 mole percent, based on the total amount of ester bonds andcarbonate bonds present. For example, 5 moles of bisphenol-A reactingcompletely with 4 moles of isophthaloyl dichloride and 1 mole ofphosgene would give a copolyester-carbonate containing 80 mole percentester bonds.

The copolyester-carbonates of the instant invention are prepared byreacting (i) at least one spiro dihydric phenol of Formula I, (ii) atleast one difunctional carboxylic acid or an ester forming reactivederivative thereof, and (iii) a carbonate precursor.

In general, any difunctional carboxylic acid or its ester formingreactive derivative conventionally used in the preparation of linearpolyesters may be utilized in the preparation of thecopolyester-carbonate polymers of the instant invention. Generally, thecarboxylic acids which may be used include the aliphatic carboxylicacids, the aromatic carboxylic acids, and the aliphatic-aromaticcarboxylic acids. These acids are disclosed in U.S. Pat. No. 3,169,121,which is hereby incorporated herein by reference.

The difunctional carboxylic acids which may be used generally willconform to the general formula

    HOOC--(R.sup.2).sub.q --COOH                               V.

wherein R² is an alkylene, alkylidene, cycloalkylene or cycloalkylidenegroup with carbon atom limitations for each R² the same as in W ofFormula II; an aromatic group such as phenylene, biphenylene,substituted phenylene, substituted biphenylene, naphthylene, substitutednaphthylene, and the like; two or more aromatic groups connected throughnon-aromatic linkages such as alkylene or alkylidene groups; and adivalent aralkyl radical such as tolylene, xylylene, and the like. Theletter q represents either zero or one.

Preferred difunctional carboxylic acids are the aromatic dicarboxylicacids, i.e., those acids of Formula V wherein R² represents a divalentaromatic radical and q is one. The preferred aromatic dicarboxylic acidsare those represented by the general formula ##STR9## wherein: R³independently selected from monovalent hydrocarbon radicals and halogenradicals; and

j is a positive integer having a value of from 0 to 4 inclusive.

The monovalent hydrocarbon radicals represented by R³ include the alkylradicals, the cycloalkyl radicals, the aryl radicals, the aralkylradicals, and the alkaryl radicals. The carbon atom limitations for eachgroup are the same as for the aforementioned R group of Formula I.

The preferred halogen radicals are the chlorine and bromine radicals.Alkyl of one to five carbon atoms in also preferred.

Particularly useful aromatic dicarboxylic acids of Formula I are thosewherein j is zero, and those wherein j is 1 to 3 and R³ is an alkylradical, preferably one containing from 1 to about 5 carbon atoms.

When more than one R³ substituent is present on the ring carbon atoms ofthe aromatic carbocyclic residue they may be the same or different.

Mixtures of these carboxylic acids may be employed in lieu of individualcarboxylic acid. Therefore, wherever the term difunctional carboxylicacid is employed herein it is meant to include mixtures of two or moredifferent difunctional carboxylic acids as well as individualdifunctional carboxylic acids.

Particularly useful aromatic dicarboxylic acids are isophthalic acid,terephthalic acid, and mixtures thereof.

Rather than utilizing the difunctional aromatic carboxylic acids per seit is possible, and sometimes even preferred, to employ the esterforming reactive derivatives of these acids. Illustrative of these esterforming reactive derivatives of these acids are the acid dihalides suchas the acid dichlorides. Thus, for example, instead of using isophthalicacid, terephthalic acid, or mixtures thereof it is possible useisophthaloyl dichloride, terephthaloyl dichloride, or mixtures thereof.

The copolyester-carbonates of the instant invention will containrepeating structural units of Formula II and those represented by thegeneral formula ##STR10## wherein R, R², n and q are as definedhereinafore.

The copolyester-carbonates of the instant invention may conveniently beprepared by the heterogeneous interfacial polymerization process. Such aprocess is disclosed, inter alia, in U.S. Pat. No. 3,169,121, which ishereby incorporated herein by reference.

The copolyester-carbonates of the instant invention may optionallycontain admixed therewith the various additives described hereinafore.

Yet another embodiment of the instant invention is acopolyester-carbonate resin derived from the coreaction of (i) acarbonate precursor, (ii) at least one difunctional carboxylic acid oran ester forming reactive derivative thereof, (iii) at least one spirodihydric phenol of Formula I, and (iv) at least one conventionalnon-spiro dihydric phenol of Formula III. In this embodiment the amountof the spiro dihydric phenol used to prepare thesecopolyester-carbonates is an amount effective to improve the heatdistortion temperatures of the copolyester-carbonates. Generally thisamount is at least about 3 mole percent, based on the total amounts ofsaid spiro dihydric phenol and said conventional non-spiro dihydricphenol used. ln general, if less than about 3 mole percent of said spirodihydric phenol is used there is no significant improvement in the heatdistortion temperatures of the copolyester-carbonates. The upper limitof the amount of said spiro dihydric phenol employed is not critical andis controlled by such secondary considerations as cost and the like. Itis generally preferred that not more than about 95 mole percent of saidspiro dihydric phenol be employed, based on the total amounts of thespiro dihydric phenol and the non-spiro dihydric phenol employed.

The copolyester-carbonates of this embodiment may optionally contain theaforedescribed additives.

Still another embodiment of the instant invention is a blend of spirodihydric phenol based copolyester-carbonates and conventional non-spirodihydric phenol based copolyester-carbonates. These blends exhibitimproved heat distortion temperatures as compared to blends ofconventional non-spiro dihydric phenol based copolyester-carbonates.

These blends are comprised of a physical mixture of (i) at least onecopolyester-carbonate derived from (a) a carbonate precursor, (b) atleast one difunctional carboxylic acid or an ester forming reactivederivative thereof, and (c) at least one spiro dihydric phenol ofFormula I (hereinafter referred to as copolyester-carbonate resin A);and (ii) at least one copolyester-carbonate derived from (a) a carbonateprecursor, (b) at least one difunctional carboxylic acid or an esterforming reactive derivative thereof, and (c) at least one conventionalnon-spiro dihydric phenol (hereinafter referred to ascopolyester-carbonate resin B).

In this embodiment the copolyester-carbonate resins A and B arepreformed and then physically mixed or blended together.

These blends contain an amount of copolyester-carbonate resin Aeffective to improve the heat distortion temperatures of the blends.Generally this amount is at least about 3 weight percent of resin A,based on the total amounts of resins A and B used. Generally if lessthan about 3 weight percent of resin A is used there will be nosignificant improvement in the heat distortion temperatures of theblends. The upper limit of the amount of resin A used is not criticalbut is generally governed by such secondary considerations as cost andthe like. Generally it is preferred that the blends contain no more thanabout 95 weight percent of the copolyester-carbonate resin A.

The instant blends may optionally have admixed therewith theaforedescribed commonly known and used additives.

DESCRIPTION OF THE PREFERRED EMBODIMENT

In order to more fully and clearly illustrate the present invention thefollowing examples are set forth. It is intended that the examples beconsidered as illustrative rather than limiting the invention asdisclosed and claimed herein. In the example all parts and percentagesare on a weight basis unless otherwise indicated.

The following example illustrates polycarbonates falling outside thescope of the instant invention. This example is presented forcomparative purposes only.

EXAMPLE 1

This example illustrates a conventional prior art polycarbonate derivedfrom bisphenol-A and phosgene.

To a 2 liter reaction vessel there are added 34.2 grams (0.15 mole) ofbisphenol-A, 0.03 gram (2.1 mole percent) of phenol, 0.42 milliliter oftriethylamine. 400 milliliters of methylene chloride and 300 millilitersof water. A 25% aqueous solution of sodium hydroxide is added to adJustthe pH of the reaction mixture to 11 and thereafter to maintain it at pH11. Into this reaction mixture are gradually introduced 18 grams ofphosgene while maintaining the pH at about 11 by the introduction ofsaid caustic solution. The methylene chloride layer is separated fromthe alkaline aqueous layer, washed with 0.01N aqueous hydrochloric acid,and is then washed twice with deionized water. The polycarbonate resinis precipitated with methanol and dried in a vacuum oven at 60° C.

The intrinsic viscosity of the resultant polycarbonate is found to be0.574 dl/gm at 25° C. in methylene chloride.

In order to determine the heat distortion temperatures of thepolycarbonate resin the glass transition temperature (Tg) of the resinis determined. As is well known to those skilled in the art the glasstransition temperatures (Tg) can generally be used in place of the heatdistortion temperatures since heat distortion temperatures are relatableto glass transition temperatures. Accordingly, glass transitiontemperatures have been measured to show resistance to high heatdistortion of the polycarbonate resins of the present invention. Theglass transition temperatures are determined by using a Perkin-ElmerDSC-2B instrument which measures the second order glass transitiontemperature or Tg by differential scanning calorimetry.

The results of this test are set forth in Table I.

The following examples illustrate the polycarbonates of the instantinvention.

EXAMPLE 2

The procedure of Example 1 is substantially repeated except that the34.2 grams of bisphenol-A are replaced with 17.1 grams of bisphenol-Aand 23.1 grams of 3,3,3',3'-tetramethyl-1,1'-spirobiindane-6,6'-diol.

The Tg of the resultant polycarbonate is determined and the results areset forth in Table I.

EXAMPLE 3

The procedure of Example 1 is substantially repeated except that the34.2 grams of bisphenol-A are replaced with 46.2 grams of3,3,3',3'-tetramethyl-1,1'-spirobiindane-6,6'-diol.

The Tg of the resultant polycarbonate is determined and the results areset forth in Table I.

                  TABLE I                                                         ______________________________________                                               Example Tg                                                                    No.     (°C.)                                                   ______________________________________                                               1 (Control)                                                                           149.0                                                                 2       183.0                                                                 3       207.2                                                          ______________________________________                                    

The following example illustrates a prior art conventionalcopolyester-carbonate. This example is presented for comparativepurposes only.

EXAMPLE 4

This example illustrates a conventional prior art copolyester-carbonatederived from isophthaloyl dichloride, bisphenol-A, and phosgene.

To a 2 liter reaction vessel there are added 34.2 grams (0.15 mole) ofbisphenol-A, 0.30 gram (2.1 mole %) of phenol, 0.42 milliliter oftriethylamine, 400 milliliters of methylene chloride and 300 millilitersof water. A 25% aqueous solution of sodium hydroxide is added to adjustthe pH of the reaction mixture to about 11 and thereafter to maintain itat a pH of about 11. Isophthaloyl dichloride, 15.2 grams (0.075 mole),dissolved in 20 grams of methylene chloride is added dropwise to thereaction mixture over a period of 5 minutes while maintaining the pH atabout 11 with the use of an automatic titrator. After the pH becomesstable, without the use of additional caustic solution, phosgene isintroduced into the reaction mixture at the rate of 0.5 gram per minutefor 26 minutes while maintaining the pH at about 11 by the addition ofthe aqueous caustic solution. The amount of phosgene added is 13 grams(0.133 mole). The methylene chloride layer is separated from thealkaline aqueous layer, washed with 0.01N aqueous hydrochloric acid, andis then washed twice with deionized water. The copolyester-carbonateresin is precipitated with methanol and dried in a vacuum oven at 60° C.

The Tg of this copolyester-carbonate is determined and the results areset forth in Table II.

The following example illustrates a copolyester-carbonate of the instantinvention.

EXAMPLE 5

This example illustrates the preparation of a copolyester-carbonate fromisophthaloyl dichloride, phosgene and a spiro dihydric phenol.

To a reactor vessel there are added 400 milliliters of methylenechloride, 300 milliliters of water, 7.7 grams of 3,3,3',3'-tetramethyl-1,1'-spirobiindane-6,6'-diol, 5.7 grams of bisphenol-A,0.07 gram of phenol, and 0.14 milliliter of triethylamine. At a pH of11, achieved by the addition of a 25% aqueous solution of sodiumhydroxide, 2.0 grams of isophthaloyl dichloride dissolved in methylenechloride are added dropwise over a 15 minute period, while maintainingthe pH at about 11 by the addition of the caustic solution. Afteraddition of the isophthaloyl dichloride is completed 5 grams of phosgeneare introduced over a 15 minute period while maintaining the pH at about11 by the use of the aqueous caustic solution. The polymer mixture isdiluted with methylene chloride and the brine phase is separated. Theresulting polymer containing phase is washed with 0.01N aqueoushydrochloric acid followed by two water washings. The polymer is thenprecipitated with methanol.

The Tg of this copolyester-carbonate is determined and the results areset forth in Table II.

                  TABLE II                                                        ______________________________________                                               Example Tg                                                                    No.     (°C.)                                                   ______________________________________                                               4 (Control)                                                                           170.6                                                                 5       201.0                                                          ______________________________________                                    

As illustrated by the data in Table I the polycarbonates of the instantinvention, i.e., Examples 2 and 3, exhibit significantly higher glasstransition temperatures than the prior art conventional polycarbonates,i.e., Example 1. The polycarbonate of Example 2, which is derived from50 mole percent of the spiro dihydric phenol and 50 mole percent ofbisphenol-A, exhibits a Tg which is 34 degrees C. higher than the priorart conventional polycarbonate of Example 1 which is derived solely frombisphenol-A.

The data of Table II also illustrate that the instantcopolyester-carbonates, i.e., Example 5, exhibit significantly higherglass transition temperatures than the conventional prior artcopolyester-carbonates, i.e., Example 4.

The instant polycarbonates and copolyester-carbonates may be used toproduce high heat resistant films and molded articles.

Other modifications and variations of the present invention are possiblein light of the above disclosure. It is, therefore, to be understoodthat changes may be made in the particular embodiments described abovewhich are in the full intended scope of the invention as defined in theappended claims.

What is claimed is:
 1. Aromatic thermoplastic polymer exhibitingimproved heat distortion temperatures derived from:(i) a carbonateprecorsor; and (ii) at least one spiro dihydric phenol selected fromspiro dihydric phenols represented by the general formula ##STR11##wherein: R is independently selected from monovalent hydrocarbonradicals or halogen radicals; andn is independently selected frompositive integers having a value of from 0 to 3 inclusive; and (iv) atleast one difunctional carboxylic acid or an ester forming reactivederivative thereof.
 2. The polymer of claim 1 wherein said difunctionalcarboxylic acid or an ester forming reactive derivative thereof is anaromatic dicarboxylic acid or an ester forming reactive derivativethereof.
 3. The polymers of claim 2 wherein said aromatic dicarboxylicacid or an ester forming reactive derivative thereof is selected fromisophthalic acid, terephthalic acid, mixtures thereof, or isophthaloyldichloride, terephthaloyl dichloride, or mixtures thereof.
 4. Thepolymer of claim 3 wherein said carbonate precursor is phosgene.
 5. Thepolymer of claim 4 wherein said monovalent hydrocarbon radicalsrepresented by R are selected from alkyl radicals, cycloalkyl radicals,aryl radicals, aralkyl radicals, or alkaryl radicals.
 6. The polymer ofclaim 5 wherein said monovalent hydrocarbon radicals are selected fromalkyl radicals.
 7. The polymer of claim 4 wherein said spiro dihydricphenol is 3,3,3', 3'-tetramethyl-1,1'-spirobiindane-6,6'-diol.
 8. Thepolymer of claim 1 which are derived from (i); (ii); (iv); and(iii) atleast one non-spiro dihydric phenol represented by the general formula##STR12## wherein: R¹ is independently selected from monovalenthydrocarbon radicals or halogen radicals;a is independently selectedfrom positive integers having a value of from 0 to 4 inclusive. d iseither zero or one; and W is selected from non-spiro divalenthydrocarbon radicals, --S--, --O--, --S--S--, ##STR13##
 9. The polymerof claim 8 wherein the amount of said spiro dihydric phenol of (ii)employed is an amount effective to improve the heat distortiontemperatures of said polymer.
 10. The polymer of claim 9 wherein saidamount is at least about 3 mole percent, based on the total amounts ofthe spiro dihydric phenol of (ii) and the non-spiro dihydric phenol of(iii) employed.
 11. The polymer of claim 9 wherein said monovalenthydrocarbon radicals represented by R are selected from alkyl radicals,cyclaolkyl radicals, aralkyl radicals, or alkaryl radicals.
 12. Thepolymer of claim 9 wherein said non-spiro divalent hydrocarbon radicalsrepresented by W are selected from alkylene radicals, cyclaolkyleneradicals, alkylidene radicals, or cycloalkylidene radicals.
 13. Thepolymer of claim 12 wherein said monovalent hydrocarbon radicalsrepresented by R¹ are selected from alkyl radicals, cycloalkyl radicals,aryl radicals, aralkyl radicals, or alkaryl radicals.
 14. The polymer ofclaim 9 wherein said difunctional carboxylic acid or an ester formingreactive derivative thereof of (iv) is an aromatic dicarboxylic acid oran ester forming reactive derivative thereof.
 15. The polymer of claim14 wherein said aromatic dicarboxylic acid or an ester forming reactivederivative thereof is selected from isophthalic acid, terephthalic acid,mixtures thereof, or isophthaloyl dichloride, terephthaloyl dichloride,or mixtures thereof.
 16. The polymer of claim 15 wherein said carbonateprecursor is phosgene.
 17. The polymer of claim 16 wherein saidnon-spiro dihydric phenol of (iii) is bisphenol-A.
 18. The polymer ofclaim 17 wherein said spiro dihydric phenol of (ii) is 3,3,3',3'-tetramethyl-1,1'-spirobiindane-6,6'-diol.